Biocide compositions (IV)

ABSTRACT

Suggested are biocide compositions, comprising (a) esters based on ketocarboxylic acids, (b) biocides, and optionally (c) oil components or co-solvents and/or (d) emulsifiers. The compositions exhibit an improved stability even if stored at temperatures between 5° and 40° C. over a longer period.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is the National Stage entry of PCT/EP 2010/005184,filed on Aug. 24, 2010, which claims priority to European Patentapplication no. 09011245.9 filed on Sep. 2, 2009, both of which areincorporated herein by reference in their entireties.

FIELD OF THE INVENTION

The present invention relates to the area of agrochemicals and refers tobiocide compositions comprising certain carboxylic acid esters and theiruse as solvents or dispersants for biocides.

BACKGROUND OF THE INVENTION

Biocides, and in particular pesticides such as fungicides, insecticidesand herbicides, are important auxiliary agents for agriculture in orderto protect crops and to increase their yield. Depending on the variousand often very specific needs a magnitude of actives exist which showvery different chemical structures and behaviours. Nevertheless, it iswell known from the state of the art that it remains difficult toprepare aqueous solutions of these actives which are exhibiting asatisfying stability, especially if stored at very low or elevatedtemperatures over a longer period. As a matter of fact, the solutionsshow a strong tendency to either separate or to form crystals, whichmakes it necessary to re-disperse the actives in the compositions priorto every application in order to obtain a homogenous product. Due to thefact that in spray equipments, which are customarily used for theapplication of aqueous formulations of plant treatment agents, severalfilters and nozzles are present, an additional problem appears which isrelated to the blocking of these filters and nozzles as a result ofcrystallizing active compound during the application of aqueous sprayliquors based on solid or amorphous active ingredients.

European patent application EP 0453899 B1 (Bayer) discloses the use ofdimethylamides derived from saturated C₆-C₂₀ fatty acids ascrystallisation inhibitors for azole derivatives which can be applied asfungicides. Unfortunately, the dimethylamides suggested in the patentare useful for a limited number of actives. Even in case of azoles andazole derivatives the ability to inhibit unwanted crystallisation islimited to ambient temperatures, while the products are close to beinguseless in case the solutions have to be used at temperatures of about 5to 10° C.

The problem underlying the present invention has been to identifysuitable new solvents for developing new biocide compositions allowingthe preparation of products with equal or higher contents of activesthan obtainable in the market. The new solvents need to be safe andenvironmental friendly and should allow obtaining concentrated biocidecompositions (on average more than 25% active matter) regardless of thechemical structure of the biocide. In particular, the compositionsshould exhibit improved solubilisation power, storage stability andreduced tendency to form crystals for a wide range of biocides within atemperature range between 0 and 40° C. Finally, another object of theinvention has been to design formulations with non-aqueous phases e.g.an emulsifiable concentrate (EC), oil-in-water emulsion (EW),suspo-emulsion (SE), with specific co-solvents and emulsifier systemproviding superior emulsion stability, in particular with respect toopacity and layering.

DETAILED DESCRIPTION OF THE INVENTION

The present invention refers to biocide compositions, comprising

-   -   (a) esters based on ketocarboxylic acids, and    -   (b) biocides, and optionally    -   (c) oil components or co-solvents and/or    -   (d) emulsifiers.

Surprisingly it has been observed that esters, preferably alkyl estersand most preferably methyl or tetrahydrofurfuryl esters obtained fromketocarboxylic acids, as for example the methyl or tetrahydrofurfurylester of 4-oxopentanoic acid (levulinic acid), show an improvedsolubilising power compared to other fatty acid derivatives as knownfrom the state of the art. Applicant has found that the ketocarboxylicacid esters are able to dissolve or disperse a wide range of biocideseven under drastic conditions, which means storage times of at least 4weeks at temperatures between 0 and 40° C. without phase separation orsedimentation. Adding oil components as co-solvents, especially thosehaving an ester structure to the compositions lead to emulsifiableconcentrates formulations showing increased emulsion behaviour andstability, in particular with respect to opacity and layering.

Ketocarboxylic Acid Esters

Esters according to the present invention (component a) can be derivedfrom ketocarboxylic acids. Preferably the esters follow the generalformula (I),R¹CO—OR²  (I)

in which R¹CO stands for R³(CH₂)_(m)CO(CH₂)_(n), R² represents alkylgroups having 1 to 4 carbon atoms or a radical of a cyclic orheterocyclic alcohol having 5 to 8 carbon atoms, R³ stands for hydrogenor an alkyl radical having 1 to 10 carbon atoms, optionally substitutedby one or more functional groups, and m and n both representindependently zero or integers of 1 to 10. The most preferred speciesexhibiting the best performance in dissolving or dispersing a widenumber of different biocides over a long period and both at low and hightemperatures are C₁-C₄ alkyl esters, in particular a methyl ester, ortetrahydrofurfuryl ester of 4-oxopentanoic acid (levulinic acid) or2-oxopropanoic acid (pyruvic acid).

Biocides

A biocide in the context of the present invention is a plant protectionagent, more particular a chemical substance capable of killing differentforms of living organisms used in fields such as medicine, agriculture,forestry, and mosquito control. Also counted under the group of biocidesare so-called plant growth regulators. Usually, biocides are dividedinto two sub-groups:

-   -   pesticides, which includes fungicides, herbicides, insecticides,        algicides, moluscicides, miticides and rodenticides, (here, The        Pesticide Handbook, 14th edition, BCPC 2006 is included as a        reference) and    -   antimicrobials, which includes germicides, antibiotics,        antibacterials, antivirals, antifungals, antiprotozoals and        antiparasites.

Biocides can also be added to other materials (typically liquids) toprotect the material from biological infestation and growth. Forexample, certain types of quaternary ammonium compounds (quats) can beadded to pool water or industrial water systems to act as an algicide,protecting the water from infestation and growth of algae.

Pesticides

The U.S. Environmental Protection Agency (EPA) defines a pesticide as“any substance or mixture of substances intended for preventing,destroying, repelling, or mitigating any pest”. A pesticide may be achemical substance or biological agent (such as a virus or bacteria)used against pests including insects, plant pathogens, weeds, mollusks,birds, mammals, fish, nematodes (roundworms) and microbes that competewith humans for food, destroy property, spread disease or are anuisance. In the following examples, pesticides suitable for theagrochemical compositions according to the present invention are given:

Fungicides. A fungicide is one of three main methods of pest control—thechemical control of fungi in this case. Fungicides are chemicalcompounds used to prevent the spread of fungi in gardens and crops.Fungicides are also used to fight fungal infections. Fungicides caneither be contact or systemic. A contact fungicide kills fungi whensprayed on its surface. A systemic fungicide has to be absorbed by thefungus before the fungus dies. Examples for suitable fungicides,according to the present invention, encompass the following chemicalclasses and corresponding examples:

-   -   Aminopyrimidines such as bupirimate,    -   Anilinopyrimidines such as cyprodinil, mepanipyrim,        pyrimethanil,    -   Heteroaromatics such as hymexazole,    -   Heteroaromatic hydrocarbons such as etridiazole,    -   Chlorophenyls/Nitroanilines such as chloroneb, dicloran,        quintozene, tecnazene, tolclofos-methyl,    -   Benzamide fungicides such as zoxamide,    -   Benzenesulfonamides such as flusulfamide,    -   Benzimidazoles such as acibenzolar, benomyl, benzothiazole,        carbendazim, fuberidazole, metrafenone, probenazole,        thiabendazole, triazoxide, and benzimidazole precursor        fungicides,    -   Carbamates such as propamocarb, diethofencarb,    -   Carboxamides such as boscalid, diclocymet, ethaboxam,        flutolanil, penthiopyrad, thifluzamide    -   Chloronitriles such chlorothalonil,    -   Cinnamic acid amides such as dimethomorph, flumorph,    -   Cyanoacetamide oximes such as cymoxanil,    -   Cyclopropancarboxamides such as carpropamid,    -   Dicarboximides such as iprodione, octhilinone, procymidone,        vinclozolin    -   Dimethyldithiocarbamates such ferbam, metam, thiram, ziram,    -   Dinitroanilines such as fluazinam,    -   Dithiocarbamates such as mancopper, mancozeb, maneb, metiram,        nabam, propineb, zineb,    -   Dithiolanes such as isoprothiolane,    -   Glucopyranosyl antibiotics such as streptomycin, validamycin,    -   Guanidines such as dodine, guazatine, iminoctadine,    -   Hexopyranosyl antibiotics such as kasugamycin,    -   Hydroxyanilides such as fenhexamid,    -   Imidazoles such as imazalil, oxpoconazole, pefurazoate,        prochloraz, triflumizole,    -   Imidazolinones such as fenamidone,    -   Inorganics such as Bordeaux mixture, copper hydroxide, copper        naphthenate, copper oleate, copper oxychloride, copper(II)        sulfate, copper sulfate, copper(II) acetate, copper(II)        carbonate, cuprous oxide, sulfur,    -   Isobenzofuranones such as phthalide,    -   Mandelamides such as mandipropamide,    -   Morpholines such as dodemorph, fenpropimorph, tridemorph,        fenpropidin, piperalin, spiroxamine, aldimorph    -   Organotins such as fentin,    -   Oxazolidinones such as oxadixyl,    -   Phenylamides such as benalaxyl, benalaxyl-M, furalaxyl,        metalaxyl, metalaxyl-M, ofurace,    -   Phenylpyrazoles such as fipronil,    -   Phenylpyrroles such as fludioxonil,    -   Phenylureas such as pencycuron,    -   Phosphonates such fosetyl,    -   Phthalamic acids such as tecloftalam,    -   Phthalimides such as captafol, captan, folpet,    -   Piperazines such as triforine,    -   Propionamides such as fenoxanil,    -   Pyridines such as pyrifenox,    -   Pyrimidines such as fenarimol, nuarimol,    -   Pyrroloquinolinones such as pyroquilon,    -   Qils such as cyazofamid,    -   Quinazolinones such as proquinazid,    -   Quinolines such as quinoxyfen,    -   Quinones such as dithianon,    -   Sulfamides such as tolylfluanid, dichlofluanid,    -   Strobilurines such as azoxystrobin, dimoxystrobin, famoxadone,        fluoxastrobin, kresoxim-methyl, metominostrobin, picoxystrobin,        pyraclostrobin, trifloxystrobin, orysastrobin,    -   Thiocarbamates such as methasulfocarb,    -   Thiophanates such as thiophanate-methyl,    -   Thiophencarboxamides such silthiofam,    -   Triazole fungicides such as azaconazole, bitertanol,        bromuconazole, cyproconazole, difenoconazole, diniconazole,        epoxiconazole, fenbuconazole, fluquinconazole, flusilazole,        flutriafol, fluotrimazole, hexaconazole, imibenconazole,        ipconazole, metconazole, myclobutanil, penconazole,        propiconazole, prothioconazole, simeconazole, tebuconazole,        tetraconazole, triadimefon, triadimenol, triticonazole,        quinconazole    -   Triazolobenzothidazoles such as tricyclazole,    -   Valinamide carbamates such as iprovalicarb, benthiavalicarb    -   Fluopicolide    -   Pentachlorophenol

and their mixtures.

Herbicides. An herbicide is a pesticide used to kill unwanted plants.Selective herbicides kill specific targets while leaving the desiredcrop relatively unharmed. Some of these act by interfering with thegrowth of the weed and are often based on plant hormones. Herbicidesused to clear waste ground are nonselective and kill all plant materialwith which they come into contact. Herbicides are widely used inagriculture and in landscape turf management. They are applied in totalvegetation control (TVC) programs for maintenance of highways andrailroads. Smaller quantities are used in forestry, pasture systems, andmanagement of areas set aside as wildlife habitat. In general, activeingredients representing including various chemical classes andcorresponding examples can be used

-   -   Anilides such as propanil    -   Aryloxycarboxylic acids e.g. MCPA-thioethyl    -   Aryloxyphenoxypropionates e.g. clodinafop-propargyl,        cyhalofop-butyl, diclofops, fluazifops, haloxyfops, quizalofops,    -   Chloroacetamides e.g. acetolochlor, alachlor, butachlor,        dimethenamid, metolachlor, propachlor    -   Cyclohexanedione oximes e.g. clethodim, sethoxydim, tralkoxydim,    -   Benzamides such as isoxaben    -   Benzimidazoles such as dicamba, ethofumesate    -   Dinitroanilines e.g. trifluralin, pendimethalin,    -   Diphenyl ethers e.g. aclonifen, oxyfluorfen,    -   The glycine derivative glyphosate, a systemic nonselective (it        kills any type of plant) herbicide used in no-till burndown and        for weed control in crops that are genetically modified to        resist its effects,    -   Hydroxybenzonitriles e.g. bromoxynil,    -   Imidazolinones e.g. fenamidone, imazapic, imazamox, imazapic,        imazapyr, imazaquin,    -   Isoxazolidinones e.g. clomazone    -   Paraquat as bypyridylium,    -   Phenyl carbamates e.g. desmedipham, phenmedipham,    -   Phenylpyrazoles e.g. pyraflufen-ethyl    -   Phenylpyrazolines e.g. pinoxaden,    -   Pyridinecarboxylic acids or synthetic auxins e.g. picloram,        clopyralid, and triclopyr,    -   Pyrimidinyloxybenzoics e.g. bispyrtbac-sodium    -   Sulfonyureas e.g. amidosulfuron, azimsulfuron,        bensulfuron-methyl, chlorsulfuron, flazasulfuron, foramsulfuron,        flupyrsulfuron-methyl-sodium, nicosulfuron, rimsulfuron,        sulfosulfuron, tribenuron-methyl, trifloxysurlfuron-sodium,        triflusulfuron, tritosulfuron,    -   Triazolopyrimidines e.g. penoxsulam, metosulam, florasulam,    -   Triketones e.g. mesotriones, sulcotrione,    -   Ureas e.g. diuron, linuron,    -   Phenoxycarboxylic acids such as 2,4-D, MCPA, MCPB, mecoprops,    -   Triazines such as atrazine, simazine, terbuthylazine,

and their mixtures.

Insecticides. An insecticide is a pesticide used against insects in alldevelopmental forms. They include ovicides and larvicides used againstthe eggs and larvae of insects. Insecticides are used in agriculture,medicine, industry and the household. In the following, suitablechemical classes and examples of insecticides are mentioned:

-   -   Abamectin, emamectin,    -   Anthranilic diamides such as rynaxypyr    -   Synthetic auxins such as avermectin,    -   Amidines such as amitraz,    -   Anthranilic diamide such as rynaxypyr,    -   Carbamates such as aldicarb, carbofuran, carbaryl, methomyl,        2-(1-methylpropyl)phenyl methylcarbamate,    -   Chlorinated insecticides such as, for example, Camphechlor, DDT,        Hexachlorocyclohexane, gamma-Hexachlorocyclohexane,        Methoxychlor, Pentachlorophenol, TDE, Aldrin, Chlordane,        Chlordecone, Dieldrin, Endosulfan, Endrin, Heptachlor, Mirex,    -   Juvenile hormone mimics such as pyriproxyfen,    -   Neonicotinoids such as imidacloprid, clothianidin, thiacloprid,        thiamethoxam,    -   Organophosphorus compounds such as acephate, azinphos-methyl,        bensulide, chlorethoxyfos, chlorpyrifos, chlorpyriphos-methyl,        diazinon, dichlorvos (DDVP), dicrotophos, dimethoate,        disulfoton, dthoprop, fenamiphos, fenitrothion, fenthion,        fosthiazate, malathion, methamidophos, methidathion,        methyl-parathion, mevinphos, naled, omethoate,        oxydemeton-methyl, parathion, phorate, phosalone, phosmet,        phostebupirim, pirimiphos-methyl, profenofos, terbufos,        tetrachlorvinphos, tribufos, trichlorfon,    -   Oxadiazines such as indoxacarb,    -   Plant toxin derived compounds such as derris (rotenone),        pyrethrum, neem (azadirachtin), nicotine, caffeine,    -   Pheromones such cuellure, methyl eugenol,    -   Pyrethroids such as, for example, allethrin, bifenthrin,        deltamethrin, permethrin, resmethrin, sumithrin, tetramethrin,        tralomethrin, transfluthrin,    -   Selective feeding blockers such as flonicamid, pymetrozine,    -   Spinosyns e.g. spinosad

and their mixtures.

Plant Growth Regulators. Plant hormones (also known as phytohormones)are chemicals that regulate plant growth. Plant hormones are signalmolecules produced within the plant, and occur in extremely lowconcentrations. Hormones regulate cellular processes in targeted cellslocally and when moved to other locations, in other locations of theplant. Plants, unlike animals, lack glands that produce and secretehormones. Plant hormones shape the plant, affecting seed growth, time offlowering, the sex of flowers, senescence of leaves and fruits. Theyaffect which tissues grow upward and which grow downward, leaf formationand stem growth, fruit development and ripening, plant longevity andeven plant death. Hormones are vital to plant growth and lacking them,plants would be mostly a mass of undifferentiated cells. In thefollowing, suitable plant growth regulators are mentioned:

-   -   Aviglycine,    -   Cyanamide,    -   Gibberellins such gibberellic acid,    -   Quaternary ammoniums such as chlormequat chloride, mepiquat        chloride,    -   Ethylene generators such ethephone,

Rodenticides. Rodenticides are a category of pest control chemicalsintended to kill rodents. Rodents are difficult to kill with poisonsbecause their feeding habits reflect their place as scavengers. Theywould eat a small bit of something and wait, and if they do not getsick, they would continue eating. An effective rodenticide must betasteless and odorless in lethal concentrations, and have a delayedeffect. In the following, examples for suitable rodenticides are given:

-   -   Anticoagulants are defined as chronic (death occurs after 1-2        weeks post ingestion of the lethal dose, rarely sooner),        single-dose (second generation) or multiple dose (first        generation) cumulative rodenticides. Fatal internal bleeding is        caused by lethal dose of anticoagulants such as brodifacoum,        coumatetralyl or warfarin. These substances in effective doses        are antivitamins K, blocking the enzymes        K₁-2,3-epoxide-reductase (this enzyme is preferentially blocked        by 4-hydroxycoumarin/4-hydroxythiacoumarin derivatives) and        K₁-quinone-reductase (this enzyme is preferentially blocked by        indandione derivatives), depriving the organism of its source of        active vitamin K₁. This leads to a disruption of the vitamin K        cycle, resulting in an inability of production of essential        blood-clotting factors (mainly coagulation factors II        (prothrombin), VII (proconvertin), IX (Christmas factor) and X        (Stuart factor)). In addition to this specific metabolic        disruption, toxic doses of        4-hydroxycoumarin/4-hydroxythiacoumarin and indandione        anticoagulants are causing damage to tiny blood vessels        (capillaries), increasing their permeability, causing diffuse        internal bleedings (haemorrhagias). These effects are gradual;        they develop in the course of days and are not accompanied by        any nociceptive perceptions, such as pain or agony. In the final        phase of intoxication the exhausted rodent collapses in        hypovolemic circulatory shock or severe anemia and dies calmly.        Rodenticidal anticoagulants are either first generation agents        (4-hydroxycoumarin type: warfarin, coumatetralyl; indandione        type: pindone, diphacinone, chlorophacinone), generally        requiring higher concentrations (usually between 0.005 and        0.1%), consecutive intake over days in order to accumulate the        lethal dose, poor active or inactive after single feeding and        less toxic than second generation agents, which are derivatives        of 4-hydroxycoumarin(difenacoum, brodifacoum, bromadiolone and        flocoumafen) or        4-hydroxy-1-benzothiin-2-one(4-hydroxy-1-thiacoumarin, sometimes        incorrectly referred to as 4-hydroxy-1-thiocoumarin, for reason        see heterocyclic compounds), namely difethialone. Second        generation agents are far more toxic than first generation        agents, they are generally applied in lower concentrations in        baits (usually in the order of 0.001-0.005%), and are lethal        after single ingestion of bait and are effective also against        strains of rodents that have become resistant against first        generation anticoagulants; thus the second generation        anticoagulants are sometimes referred to as “superwarfarins”.        Sometimes, anticoagulant rodenticides are potentiated by an        antibiotic, most commonly by sulfaquinoxaline. The aim of this        association (e.g. warfarin 0.05%+sulfaquinoxaline 0.02%, or        difenacoum 0.005%+sulfaquinoxaline 0.02% etc.) is that the        antibiotic/bacteriostatic agent suppresses intestinal/gut        symbiotic microflora that represents a source of vitamin K. Thus        the symbiotic bacteria are killed or their metabolism is        impaired and the production of vitamin K by them is diminuted,        an effect which logically contributes to the action of        anticoagulants. Antibiotic agents other than sulfaquinoxaline        may be used, for example co-trimoxazole, tetracycline, neomycin        or metronidazole. A further synergism used in rodenticidal baits        is that of an association of an anticoagulant with a compound        with vitamin D-activity, i.e. cholecalciferol or ergocalciferol        (see below). A typical formula used is, e. g., warfarin        0.025-0.05%+cholecalciferol 0.01%. In some countries there are        even fixed three-component rodenticides, i.e.        anticoagulant+antibiotic+vitamin D, e. g. difenacoum        0.005%+sulfaquinoxaline 0.02%+cholecalciferol 0.01%.        Associations of a second-generation anticoagulant with an        antibiotic and/or vitamin D are considered to be effective even        against the most resistant strains of rodents, though some        second generation anticoagulants (namely brodifacoum and        difethialone), in bait concentrations of 0.0025-0.005% are so        toxic that no known resistant strain of rodents exists and even        rodents resistant against any other derivatives are reliably        exterminated by application of these most toxic anticoagulants.

Vitamin K₁ has been suggested and successfully used as an antidote forpets or humans, which/who were either accidentally or intentionally(poison assaults on pets, suicidal attempts) exposed to anticoagulantpoisons. In addition, since some of these poisons act by inhibitingliver functions and in progressed stages of poisoning, severalblood-clotting factors as well as the whole volume of circulating bloodlacks, a blood transfusion (optionally with the clotting factorspresent) can save a person's life who inadvertently takes them, which isan advantage over some older poisons.

-   -   Metal phosphides have been used as a means of killing rodents        and are considered single-dose fast acting rodenticides (death        occurs commonly within 1-3 days after single bait ingestion). A        bait consisting of food and a phosphide (usually zinc phosphide)        is left where the rodents can eat it. The acid in the digestive        system of the rodent reacts with the phosphide to generate the        toxic phosphine gas. This method of vermin control has possible        use in places where rodents are resistant to some of the        anticoagulants, particularly for control of house and field        mice; zinc phosphide baits are also cheaper than most        second-generation anticoagulants, so that sometimes, in cases of        large infestation by rodents, their population is initially        reduced by copious amounts of zinc phosphide bait applied, and        the rest of the population that survived the initial fast-acting        poison is then eradicated by prolonged feeding on anticoagulant        bait. Inversely, the individual rodents that survived        anticoagulant bait poisoning (rest population) can be eradicated        by pre-baiting them with nontoxic bait for a week or two (this        is important to overcome bait shyness, and to get rodents used        to feeding in specific areas by offering specific food,        especially when eradicating rats) and subsequently applying        poisoned bait of the same sort as used for pre-baiting until all        consumption of the bait ceases (usually within 2-4 days). These        methods of alternating rodenticides with different modes of        action provides a factual or an almost 100% eradication of the        rodent population in the area if the acceptance/palatability of        bait is good (i.e., rodents readily feed on it).    -   Phosphides are rather fast acting rat poisons, resulting in that        the rats are dying usually in open areas instead of the affected        buildings. Typical examples are aluminum phosphide (fumigant        only), calcium phosphide (fumigant only), magnesium phosphide        (fumigant only) and zinc phosphide (in baits). Zinc phosphide is        typically added to rodent baits in amounts of around 0.75-2%.        The baits have a strong, pungent garlic-like odor characteristic        for phosphine liberated by hydrolysis. The odor attracts (or, at        least, does not repulse) rodents, but has a repulsive effect on        other mammals; birds, however (notably wild turkeys), are not        sensitive to the smell and feed on the bait thus becoming        collateral damage.    -   Hypercalcemia. Calciferols (vitamins D), cholecalciferol        (vitamin D₃) and ergocalciferol (vitamin D₂) are used as        rodenticides, which are toxic to rodents for the same reason        that they are beneficial to mammals: they are affecting calcium        and phosphate homeostasis in the body. Vitamins D are essential        in minute quantities (few IUs per kilogram body weight daily,        which is only a fraction of a milligram), and like most fat        soluble vitamins they are toxic in larger doses as they readily        result in the so-called hypervitaminosis, which is, simply said,        poisoning by the vitamin. If the poisoning is severe enough        (that is, if the dose of the toxicant is high enough), it        eventually leads to death. In rodents consuming the rodenticidal        bait it causes hypercalcemia by raising the calcium level,        mainly by increasing calcium absorption from food, mobilising        bone-matrix-fixed calcium into ionised form (mainly        monohydrogencarbonate calcium cation, partially bound to plasma        proteins,

[CaHCO₃]⁺), which circulates dissolved in the blood plasma, and afteringestion of a lethal dose the free calcium levels are raisedsufficiently so that blood vessels, kidneys, the stomach wall and lungsare mineralised/calcificated (formation of calcificates, crystals ofcalcium salts/complexes in the tissues thus damaging them), leadingfurther to heart problems (myocard is sensitive to variations of freecalcium levels that are affecting both myocardial contractibility andexcitation propagation between atrias and ventriculas) and bleeding (dueto capillary damage) and possibly kidney failure. It is considered to besingle-dose, or cumulative (depending on concentration used; the common0.075% bait concentration is lethal to most rodents after a singleintake of larger portions of the bait), sub-chronic (death occurringusually within days to one week after ingestion of the bait). Appliedconcentrations are 0.075% cholecalciferol and 0.1% ergocalciferol whenused alone. There is an important feature of calciferols toxicologywhich is that they are synergistic with anticoagulant toxicants. Thismeans that mixtures of anticoagulants and calciferols in the same baitare more toxic than the sum of toxicities of the anticoagulant and thecalciferol in the bait so that a massive hypercalcemic effect can beachieved by a substantially lower calciferol content in the bait andvice-versa. More pronounced anticoagulant/hemorrhagic effects areobserved if calciferol is present. This synergism is mostly used inbaits low in calciferol because effective concentrations of calciferolsare more expensive than effective concentrations of most anticoagulants.The historically very first application of a calciferol in rodenticidalbait was, in fact, the Sorex product Sorexa® D (with a different formulathan today's Sorexa® D) back in the early 1970′s, containing warfarin0.025%+ergocalciferol 0.1%. Today, Sorexa® CD contains a 0.0025%difenacoum+0.075% cholecalciferol combination. Numerous other brandproducts containing either calciferols 0.075-0.1% (e. g. Quintox®,containing 0.075% cholecalciferol) alone, or a combination of calciferol0.01-0.075% with an anticoagulant are marketed.

Miticides, moluscicides and nematicides. Miticides are pesticides thatkill mites. Antibiotic miticides, carbamate miticides, formamidinemiticides, mite growth regulators, organochlorine, permethrin andorganophosphate miticides all belong to this category. Molluscicides arepesticides used to control mollusks, such as moths, slugs and snails.These substances include metaldehyde, methiocarb and aluminium sulfate.A nematicide is a type of chemical pesticide used to kill parasiticnematodes (a phylum of worm). A nematicide is obtained from a neemtree's seed cake; which is the residue of neem seeds after oilextraction. The neem tree is known by several names in the world but wasfirst cultivated in India since ancient times.

Antimicrobials

In the following examples, antimicrobials suitable for agrochemicalcompositions according to the present invention are given. Bactericidaldisinfectants mostly used are those applying

-   -   active chlorine (i.e., hypochlorites, chloramines,        dichloroisocyanurate and trichloroisocyanurate, wet chlorine,        chlorine dioxide, etc.),    -   active oxygen (peroxides such as peracetic acid, potassium        persulfate, sodium perborate, sodium percarbonate and urea        perhydrate),    -   iodine (iodpovidone (povidone-iodine, Betadine), Lugol's        solution, iodine tincture, iodinated nonionic surfactants),    -   concentrated alcohols (mainly ethanol, 1-propanol, called also        n-propanol and 2-propanol, called isopropanol and mixtures        thereof; further, 2-phenoxyethanol and 1- and 2-phenoxypropanols        are used),    -   phenolic substances (such as phenol (also called “carbolic        acid”), cresols (called “Lysole” in combination with liquid        potassium soaps), halogenated (chlorinated, brominated) phenols,        such as hexachlorophene, triclosan, trichlorophenol,        tribromophenol, pentachlorophenol, Dibromol and salts thereof),    -   cationic surfactants such as some quaternary ammonium cations        (such as benzalkonium chloride, cetyl trimethylammonium bromide        or chloride, didecyldimethylammonium chloride, cetylpyridinium        chloride, benzethonium chloride) and others, non-quarternary        compounds such as chlorhexidine, glucoprotamine, octenidine        dihydrochloride, etc.),    -   strong oxidizers such as ozone and permanganate solutions;    -   heavy metals and their salts such as colloidal silver, silver        nitrate, mercury chloride, phenylmercury salts, copper sulfate,        copper oxide-chloride etc. Heavy metals and their salts are the        most toxic and environmentally hazardous bactericides and,        therefore, their use is strongly suppressed or forbidden;        further, also    -   properly concentrated strong acids (phosphoric, nitric,        sulfuric, amidosulfuric, toluenesulfonic acids) and    -   alcalis (sodium, potassium, calcium hydroxides) between pH<1        or >13, particularly below elevated temperatures (above 60° C.)        kill bacteria.

As antiseptics (i.e., germicide agents that can be used on human oranimal body, skin, mucoses, wounds and the like), few of the abovementioned disinfectants can be used under proper conditions (mainlyconcentration, pH, temperature and toxicity toward man/animal). Amongthem, important are

-   -   Some properly diluted chlorine preparations (e. g. Daquin's        solution, 0.5% sodium or potassium hypochlorite solution,        pH-adjusted to pH 7-8, or 0.5-1% solution of sodium        benzenesulfochloramide (chloramine B)), some    -   iodine preparations such as iodopovidone in various galenics        (ointments, solutions, wound plasters), in the past also Lugol's        solution,    -   peroxides as urea perhydrate solutions and pH-buffered 0.1-0.25%        peracetic acid solutions,    -   alcohols with or without antiseptic additives, used mainly for        skin antisepsis,    -   weak organic acids such as sorbic acid, benzoic acid, lactic        acid and salicylic acid    -   some phenolic compounds such as hexachlorophene, triclosan and        Dibromol, and    -   cation-active compounds such as 0.05-0.5% benzalkonium, 0.5-4%        chlorhexidine, 0.1-2% octenidine solutions.

Bactericidal antibiotics kill bacteria; bacteriostatic antibiotics onlyslow down their growth or reproduction. Penicillin is a bactericide, asare cephalosporins. Aminoglycosidic antibiotics can act in both abactericidic manner (by disrupting cell wall precursor leading to lysis)or bacteriostatic manner (by connecting to 30 s ribosomal subunit andreducing translation fidelity leading to inaccurate protein synthesis).Other bactericidal antibiotics according to the present inventioninclude the fluoroquinolones, nitrofurans, vancomycin, monobactams,co-trimoxazole, and metronidazole Preferred actives are those withsystemic or partially systemic mode of action such as for exampleazoxystrobin.

Overall preferred are biocides selected from the group consisting ofglyphosate and its salts, glufosinate and its salts.

Oil Components

In a number of cases it is advantageous to add oil components (optionalcomponent c) to the biocide compositions in order to support theemulsification power of the products. Suitable products comprise Guerbetalcohols based on fatty alcohols having 6 to 18, preferably 8 to 10,carbon atoms, esters of linear C₆-C₂₂-fatty acids with linear orbranched C₆-C₂₂-fatty alcohols or esters of branched C₆-C₁₃-carboxylicacids with linear or branched C₆-C₂₂-fatty alcohols, such as, forexample, myristyl myristate, myristyl palmitate, myristyl stearate,myristyl isostearate, myristyl oleate, myristyl behenate, myristylerucate, cetyl myristate, cetyl palmitate, cetyl stearate, cetylisostearate, cetyl oleate, cetyl behenate, cetyl erucate, stearylmyristate, stearyl palmitate, stearyl stearate, stearyl isostearate,stearyl oleate, stearyl behenate, stearyl erucate, isostearyl myristate,isostearyl palmitate, isostearyl stearate, isostearyl isostearate,isostearyl oleate, isostearyl behenate, isostearyl oleate, oleylmyristate, oleyl palmitate, oleyl stearate, oleyl isostearate, oleyloleate, oleyl behenate, oleyl erucate, behenyl myristate, behenylpalmitate, behenyl stearate, behenyl isostearate, behenyl oleate,behenyl behenate, behenyl erucate, erucyl myristate, erucyl palmitate,erucyl stearate, erucyl isostearate, erucyl oleate, erucyl behenate anderucyl erucate. Also suitable are esters of linear C₆-C₂₂-fatty acidswith branched alcohols, in particular 2-ethylhexanol, esters ofC₁₈-C₃₈-alkylhydroxy carboxylic acids with linear or branchedC₆-C₂₂-fatty alcohols, in particular Dioctyl Malate, esters of linearand/or branched fatty acids with polyhydric alcohols (such as, forexample, propylene glycol, dimerdiol or trimertriol) and/or Guerbetalcohols, triglycerides based on C₆-C₁₀-fatty acids, liquidmono-/di-/triglyceride mixtures based on C₆-C₁₈-fatty acids, esters ofC₆-C₂₂-fatty alcohols and/or Guerbet alcohols with aromatic carboxylicacids, in particular benzoic acid, esters of C₂-C₁₂-dicarboxylic acidswith linear or branched alcohols having 1 to 22 carbon atoms (Cetiol®B)or polyols having 2 to 10 carbon atoms and 2 to 6 hydroxyl groups,vegetable oils, branched primary alcohols, substituted cyclohexanes,linear and branched C₆-C₂₂-fatty alcohol carbonates, such as, forexample, Dicaprylyl Carbonate (Cetiol® CC), Guerbet carbonates, based onfatty alcohols having 6 to 18, preferably 8 to 10, carbon atoms, estersof benzoic acid with linear and/or branched C₆-C₂₂-alcohols (e.g.Cetiol® AB), linear or branched, symmetrical or asymmetrical dialkylethers having 6 to 22 carbon atoms per alkyl group, such as, forexample, dicaprylyl ether (Cetiol® OE), ring-opening products ofepoxidized fatty acid esters with polyols, silicone oils(cyclomethicones, silicone methicone grades, etc.), aliphatic ornaphthenic hydrocarbons, such as, for example, squalane, squalene ordialkylcyclohexanes, and/or mineral oils. The preferred oilcomponents/co-solvents show an ester structure preferably adipates(Cetiol® B, Agnique DiME 6), methyl esters of vegetable oils (Agnique®ME 18RD-F, Agnique® ME 12C-F), alkyl esters (Agnique® Ae 3-2EH), allproducts available in the market from Cognis GmbH.

Emulsifiers

In a number of cases it is advantageous to add emulsifiers (optionalcomponent d) to the biocide compositions in order to support thestability of the products. A first preferred group of emulsifiersencompasses non-ionic surfactants such as, for example:

-   -   products of the addition of 2 to 30 mol ethylene oxide and/or 0        to 5 mol propylene oxide onto linear C₈₋₂₂ fatty alcohols, onto        C₁₂₋₂₂ fatty acids and onto alkyl phenols containing 8 to 15        carbon atoms in the alkyl group;    -   C_(12/18) fatty acid monoesters and diesters of addition        products of 1 to 30 mol ethylene oxide onto glycerol;

glycerol mono- and diesters and sorbitan mono- and diesters of saturatedand unsaturated fatty acids containing 6 to 22 carbon atoms and ethyleneoxide addition products thereof;

-   -   addition products of 15 to 60 mol ethylene oxide onto castor oil        and/or hydrogenated castor oil;    -   polyol esters and, in particular, polyglycerol esters such as,        for example, polyglycerol polyricinoleate, polyglycerol        poly-12-hydroxystearate or polyglycerol dimerate isostearate.        Mixtures of compounds from several of these classes are also        suitable;    -   addition products of 2 to 15 mol ethylene oxide onto castor oil        and/or hydrogenated castor oil;    -   partial esters based on linear, branched, unsaturated or        saturated C_(6/22) fatty acids, ricinoleic acid and        12-hydroxystearic acid and glycerol, polyglycerol,        pentaerythritol, -dipentaerythritol, sugar alcohols (for example        sorbitol), alkyl glucosides (for example methyl glucoside, butyl        glucoside, lauryl glucoside) and polyglucosides (for example        cellulose);    -   alkoxylatation products of saccharose esters    -   mono-, di and trialkyl phosphates and mono-, di- and/or        tri-PEG-alkyl phosphates and salts thereof;    -   wool wax alcohols;    -   polysiloxane/polyalkyl polyether copolymers and corresponding        derivatives;    -   mixed esters of pentaerythritol, fatty acids, citric acid and        fatty alcohol and/or mixed esters of C₆₋₂₂ fatty acids, methyl        glucose and polyols, preferably glycerol or polyglycerol,    -   polyalkylene glycols and    -   glycerol carbonate.

The addition products of ethylene oxide and/or propylene oxide ontofatty alcohols, fatty acids, alkylphenols, glycerol mono- and diestersand sorbitan mono- and diesters of fatty acids or onto castor oil areknown commercially available products. They are homologue mixtures ofwhich the average degree of alkoxylation corresponds to the ratiobetween the quantities of ethylene oxide and/or propylene oxide andsubstrate with which the addition reaction is carried out. C_(12/18)fatty acid monoesters and diesters of addition products of ethyleneoxide onto glycerol are known as lipid layer enhancers for cosmeticformulations. The preferred emulsifiers are described in more detail asfollows:

Partial Glycerides

Typical examples of suitable partial glycerides are hydroxystearic acidmonoglyceride, hydroxystearic acid diglyceride, isostearic acidmonoglyceride, isostearic acid diglyceride, oleic acid monoglyceride,oleic acid diglyceride, ricinoleic acid monoglyceride, ricinoleic aciddiglyceride, linoleic acid monoglyceride, linoleic acid diglyceride,linolenic acid monoglyceride, linolenic acid diglyceride, erucic acidmonoglyceride, erucic acid diglyceride, tartaric acid monoglyceride,tartaric acid diglyceride, citric acid monoglyceride, citric aciddiglyceride, malic acid monoglyceride, malic acid diglyceride andtechnical mixtures thereof which may still contain small quantities oftriglyceride from the production process. Addition products of 1 to 30,and preferably 5 to 10, mol ethylene oxide onto the partial glyceridesmentioned are also suitable.

Sorbitan Esters

Suitable sorbitan esters are sorbitan monoisostearate, sorbitansesquiisostearate, sorbitan diisostearate, sorbitan triisostearate,sorbitan monooleate, sorbitan sesquioleate, sorbitan dioleate, sorbitantrioleate, sorbitan monoerucate, sorbitan sesquierucate, sorbitandierucate, sorbitan trierucate, sorbitan monoricinoleate, sorbitansesquiricinoleate, sorbitan diricinoleate, sorbitan triricinoleate,sorbitan monohydroxystearate, sorbitan sesquihydroxystearate, sorbitandihydroxystearate, sorbitan trihydroxystearate, sorbitan monotartrate,sorbitan sesquitartrate, sorbitan ditartrate, sorbitan tritartrate,sorbitan monocitrate, sorbitan sesquicitrate, sorbitan dicitrate,sorbitan tricitrate, sorbitan monomaleate, sorbitan sesquimaleate,sorbitan dimaleate, sorbitan trimaleate and technical mixtures thereof.Addition products of 1 to 30, and preferably 5 to 10, mol ethylene oxideonto the sorbitan esters mentioned are also suitable.

Polyglycerol Esters

Typical examples of suitable polyglycerol esters are Polyglyceryl-2Dipolyhydroxystearate (Dehymuls® PGPH), Polyglycerin-3-Diisostearate(Lameform® TGI), Polyglyceryl-4 Isostearate (Isolan® GI 34),Polyglyceryl-3 Oleate, Diisostearoyl Polyglyceryl-3 Diisostearate(Isolan® PDI), Polyglyceryl-3 Methylglucose Distearate (Tego Care® 450),Polyglyceryl-3 Beeswax (Cera Belling), Polyglyceryl-4 Caprate(Polyglycerol Caprate T2010/90), Polyglyceryl-3 Cetyl Ether (Chimexane®NL), Polyglyceryl-3 Distearate (Cremophor® GS 32) and PolyglycerylPolyricinoleate (Admul® WOL 1403), Polyglyceryl Dimerate Isostearate andmixtures thereof. Examples of other suitable polyolesters are the mono-,di- and triesters of trimethylol propane or pentaerythritol with lauricacid, cocofatty acid, tallow fatty acid, palmitic acid, stearic acid,oleic acid, behenic acid and the like, optionally reacted with 1 to 30mol ethylene oxide.

Alk(en)yl Oligoglycosides

The alkyl or alkenyl oligoglycosides representing also preferredemulsifiers may be derived from aldoses or ketoses containing 5 or 6carbon atoms, preferably glucose. Accordingly, the preferred alkyland/or alkenyl oligoglycosides are alkyl or alkenyl oligoglucosides.These materials are also known generically as “alkyl polyglycosides”(APG). The alk(en)yl oligoglycosides according to the inventioncorrespond to formula (II):R⁴O[G]_(p)  (II)wherein R⁴ is an alkyl or alkenyl radical having from 6 to 22 carbonatoms, G is a sugar unit having 5 or 6 carbon atoms and p is a numberfrom 1 to 10. The index p in general formula (II) indicates the degreeof oligomerisation (DP degree), i.e. the distribution of mono- andoligoglycosides, and is a number of 1 to 10. Whereas p in a givencompound must always be an integer and, above all, may assume a value of1 to 6, the value p for a certain alkyl oligoglycoside is ananalytically determined calculated quantity which is mostly a brokennumber. Alk(en)yl oligoglycosides having an average degree ofoligomerisation p of 1.1 to 3.0 are preferably used. Alk(en)yloligoglycosides having a degree of oligomerisation below 1.7 and, moreparticularly, between 1.2 and 1.4 are preferred from the applicationalpoint of view. The alkyl or alkenyl radical R⁵ may be derived fromprimary alcohols containing 4 to 22 and preferably 8 to 16 carbon atoms.Typical examples are butanol, caproic alcohol, caprylic alcohol, capricalcohol, undecyl alcohol, lauryl alcohol, myristyl alcohol, cetylalcohol, palmitoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleylalcohol, elaidyl alcohol, petroselinyl alcohol, arachyl alcohol,gadoleyl alcohol, behenyl alcohol, erucyl alcohol and technical mixturesthereof such as are formed, for example, in the hydrogenation oftechnical fatty acid methyl esters or in the hydrogenation of aldehydesfrom Roelen's oxo synthesis. Alkyl oligoglucosides based on hydrogenatedC₈-C₁₆ coconut oil alcohol having a DP of 1 to 3 are preferred. Alsosuitable are alkoxylation products of alkyl oligoglucosides, for exampleadducts of 1 to 10 moles ethylene oxide and/or 1 to 5 moles propyleneoxide to C₈-C₁₀ or C₁₂-C₁₈ alkyl oligoglucoside having a DP between 1.2and 1.4.Miscellaneous Emulsifiers

Typical anionic emulsifiers are aliphatic C₁₂₋₂₂ fatty acids such aspalmitic acid, stearic acid or behenic acid, for example, and C₁₂₋₂₂dicarboxylic acids such as azelaic acid or sebacic acid, for example.Other suitable emulsifiers are zwitterionic surfactants. Zwitterionicsurfactants are surface-active compounds which contain at least onequaternary ammonium group and at least one carboxylate and one sulfonategroup in the molecule. Particularly suitable zwitterionic surfactantsare the so-called betaines such as the N-alkyl-N,N-dimethyl ammoniumglycinates, for example cocoalkyl dimethyl ammonium glycinate,N-acylaminopropyl-N,N-dimethyl ammonium glycinates, for examplecocoacylaminopropyl dimethyl ammonium glycinate, and2-alkyl-3-carboxymethyl-3-hydroxyethyl imidazolines containing 8 to 18carbon atoms in the alkyl or acyl group and cocoacylaminoethylhydroxyethyl carboxymethyl glycinate. The fatty acid amide derivativeknown under the CTFA name of Cocamidopropyl Betaine is particularlypreferred. Ampholytic surfactants are also suitable emulsifiers.Ampholytic surfactants are surface-active compounds which, in additionto a C_(8/18) alkyl or acyl group, contain at least one free amino groupand at least one —COOH— or —SO₃H— group in the molecule and which arecapable of forming inner salts. Examples of suitable ampholyticsurfactants are N-alkyl glycines, N-alkyl propionic acids,N-alkylaminobutyric acids, N-alkyliminodipropionic acids,N-hydroxyethyl-N-alkylamidopropyl glycines, N-alkyl taurines, N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acidscontaining around 8 to 18 carbon atoms in the alkyl group. Particularlypreferred ampholytic surfactants are N-cocoalkylaminopropionate,cocoacylaminoethyl aminopropionate and C_(12/18) acyl sarcosine.

Biocide Compositions

Depending on the nature of the biocide the products may show thefollowing compositions:

-   -   (a) about 0.1% b.w. to about 99% b.w., preferably about 15% b.w.        to about 70% b.w., and most preferably about 20% b.w. to about        45% b.w., esters derived from ketocarboxylic acids,    -   (b) about 1% b.w. to about 99.1% b.w., preferably about 5% b.w.        to about 75% b.w., and most preferably about 15% b.w. to about        40% b.w., biocides,    -   (c) 0 to about 50, preferably about 5 to about 30 and more        preferably about 10 to about 25% b.w. oil components/co-solvents        and    -   (d) 0% b.w. to about 15% b.w., and preferably 5 to 10% b.w.,        emulsifiers

on condition that the numbers add to 100% b.w. The compositions arepesticides concentrates to be diluted with water to give a aqueousformulations for end-users comprising about 0.5 to about 5, preferablyabout 0.5 to about 1% of the active matter represented by theconcentrate.

Industrial Application

A final embodiment of the present invention is related to the use ofesters based on ketocarboxylic acids, in particular C₁-C₄ alkyl ortetrahydrofurfuryl esters based on 4-oxopentanoic acid (levulinic acid)as solvents or dispersants for biocides.

EXAMPLES Examples 1 to 6, Comparative Examples C1 and C2 Stability

Several aqueous concentrates were prepared by mixing biocides, solventsand emulsifiers in water until a homogeneous solution was obtained. Theconcentrates were subsequently diluted with water in order to achieve anactive matter concentration of 10% b.w. The products thus obtained werestored over a period of 10 to 40 days at temperatures of 5, 20 and 40°C. The stability of the mixtures was observed by inspection anddetermined according to the following scale: (++)=stable; (+)=slightphase separation/formation of some crystals; (o)=significant phaseseparation/sedimentation; (−) phases clearly separated/strongsedimentation of crystals. The results are compiled in Table 1. Theamounts reflect the composition of the concentrates.

TABLE 1 Stability of biocide compositions Composition [% b.w.] 1 2 3 4 56 C1 C2 Glyphosate (IPA salt) 35 — — — — — — — Glyphosate (K salt) — 35— — 25 — 35 — Glufosinate — — 35 — — 25 — 35 Deltametrin — — — 35 — — —— Levulinic acid 25 25 25 25 10 10 — — tetrahydrofurfuryl ester Oleicacid methyl ester — — — — — — 25 — Stearic acid dimethylamide — — — — —— — 25 Sorbitanmono/dilaurate + 20EO 10 10 10 10 10 10 10 10 Water add100 Stability after 10 days, 5° C. ++ ++ ++ ++ ++ ++ + ++ after 20 days,5° C. ++ ++ ++ ++ ++ ++ + ++ after 40 days, 5° C. ++ ++ ++ ++ ++ ++ ∘ +after 10 days, 20° C. ++ ++ ++ ++ ++ ++ + ++ after 20 days, 20° C. ++ ++++ ++ ++ ++ + + after 40 days, 20° C. + + + + + + + + after 10 days, 40°C. ++ ++ ++ ++ ++ ++ + + after 20 days, 40° C. + + + + + + + ∘ after 40days, 40° C. + + ∘ ∘ + + ∘ ∘

Example 7, Comparative Examples C3 and C4 Solubility

Solubility of two fungicides, one herbicide and one insecticide indifferent solvents at 25° C. was tested. The results, including minimumtarget solubility for each biocide is presented in Table 2.

TABLE 2 Solubility of biocides [% b.w.] Tebuco- Epoxi- Oxy- Ex. Solventsnazole conazole fluorfen Novaluron Minimum target solubility 30 12.5 2515 7 Levulinic acid 40 18 33 24 tetrahydrofurfuryl ester C3 C₈-C₁₀ fattyacid 38 9 31 32 dimethylamide C4 Lactic acid dimethyl 35 15 23 22 amide

What is claimed is:
 1. A biocide composition comprising: (a) a levulinicacid tetrahydrofurfuryl ester and (b) a biocide selected from the groupconsisting of triazoles, glyphosate and its salts, glufosinate,deltamethrin and tebuconazole.
 2. The biocide composition according toclaim 1, further comprising component (c) an oil component or aco-solvent.
 3. The biocide composition according to claim 1, furthercomprising component (d) an emulsifier.
 4. The biocide compositionaccording to claim 1 comprising: (a) 0.1% b.w. to 99% b.w. of thelevulinic acid tetrahydrofurfuryl ester, (b) 1% b.w. to 99.1% b.w. ofthe biocide, (c) 0 to 50% b.w. of an oil component and/or a co-solvent,and (d) 0% to 15% b.w. of an emulsifier and/or a dispersing additive, oncondition that the amounts add—optionally with water or polyols—to 100%b.w.
 5. The biocide composition according to claim 1 comprising thebiocide in an amount of 5% b.w. to 50% b.w.
 6. A method comprising:providing a levulinic acid tetrahydrofurfuryl ester, mixing thelevulinic acid tetrahydrofurfuryl ester with a biocide selected from thegroup consisting of triazoles, glyphosate and its salts, glufosinate,deltamethrin and tebuconazole, wherein the levulinic acidtetrahydrofurfuryl ester is effective as a solvent or dispersant for thebiocide.
 7. The biocide composition of claim 1 having a mean storagetime of at least 4 weeks at temperatures between 0 and 40° C. withoutphase separation or sedimentation.